Method for fabricating a high-activity double-metal-cyanide catalyst

ABSTRACT

A high-activity double-metal-cyanide catalyst, a method for fabricating the same, and applications of the same are disclosed. An organic complexing ligand, which is formed via mixing fatty alcohols and alicyclic carbonates, is used to generate a high-activity double-metal-cyanide catalyst. The high-activity double-metal-cyanide catalyst includes at least one double-metal-cyanide compound, at least one organic complexing ligand, and an optional functionalized compound. The double-metal-cyanide catalyst of the present invention has a higher activity than the conventional double-metal-cyanide catalysts. The polyols generated by the present invention has an insignificant amount of high-molecular-weight compounds.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation-in-Part of co-pending applicationSer. No. 16/202,497, filed on Nov. 28, 2018, which is a Divisional ofco-pending application Ser. No. 15/847,344 filed on Dec. 19, 2017, forwhich priority is claimed under 35 U.S.C. § 120, the entire contents ofwhich are hereby incorporated by reference.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates to a high-activity double-metal-cyanide(DMC) catalyst, particularly to a technology using an alicycliccarbonate as the constituent of the organic complexing ligand to enhancethe activity of a DMC catalyst and using the high-activity DMC catalystto produce polyols containing an insignificant amount ofhigh-molecular-weight components.

Description of the Related Art

The double-metal-cyanide (DMC) catalyst can function as a superiorcatalyzing agent of the polymerization of epoxides. The DMC catalyst hashigh activity. The polyols fabricated with the DMC catalyst has a lowerunsaturation level than that fabricated with the potassium hydroxide(KOH) catalyst. The DMC catalyst may be used to fabricate polyetherpolyols, polyester polyols, polyether-ester polyols, which are mostlyapplied to polyurethane coatings, elastomers, sealants, foams andadhesives.

The typical methods of fabricating DMC are using an aqueous solutionreaction of metal salts and metal cyanide salts to form deposition ofDMC, such as the methods disclosed in U.S. Pat. Nos. 3,427,256,3,289,505 and 5,158,922. Some improved DMC fabrication methods useorganic complexing ligands to make DMC having appropriate activity, suchas the methods disclosed in U.S. Pat. Nos. 3,278,459, 3,829,505,4,477,589 and 5,470,813. Some DMC fabrication methods add functionalizedpolymers to further enhance the activity of DMC, such as the methodsdisclosed in U.S. Pat. Nos. 5,482,908, 5,545,601 and 5,627,120. Incomparison with the KOH-based methods, the DMC-based methods haveadvantages of high reaction speed and low unsaturation level. However,the polyols fabricated by the DMC-based methods contain morehigh-molecular-weight compounds, such as the compounds having an averagemolecular weight higher than 400000. The high-molecular-weight compoundswill reduce the workability after the polyols are processed. Forexample, after processing, the polyols become tight foam, or the foamthereof is easy to settle or collapse. Many methods were proposed toovercome the abovementioned problems, such as redesigning the formula ofpolyurethane or removing high-molecular-weight compounds from polyols.However, these methods are too expensive to apply industrially.

SUMMARY OF THE INVENTION

The primary objective of the present invention is to provide ahigh-activity double-metal-cyanide (DMC) catalyst, a method forfabricating the same, and applications of the same. The presentinvention uses an alicyclic carbonate as the constituent of the organiccomplexing ligand to fabricate a high-activity DMC catalyst. In additionto increasing the activity of the DMC catalyst, the present inventionalso decrease the amount of high-molecular-weight compounds in polyols.

In order to achieve the abovementioned objective, the present inventionproposes a high-activity double-metal-cyanide (DMC) catalyst, whichcomprises at least one double-metal-cyanide compound and at least oneorganic complexing ligand, wherein the organic complexing ligand is amixture of a C2-C7 fatty alcohol and an alicyclic carbonate, and whereinthe concentration of the fatty alcohol in the organic complexing ligandis 2-98 mole %. The alicyclic carbonate of the organic complexing ligandhas a structural formula expressed by chemical formula (I):

wherein R and R′ may be the same or different, and wherein each of R andR′ is selected from a group consisting of hydrogen atoms, saturatedalkyl groups each containing 1-20 carbon atoms, cyclic alkyl groups,hydroxyl groups, and vinyl groups.

The double metal cyanide of the abovementioned high-activitydouble-metal-cyanide catalyst is the product of the reaction of at leastone metal salt and at least one metal cyanide salt.

The metal salt has a general formula expressed by chemical formula (II):M(X)_(n)  (II)

wherein M in chemical formula (II) is selected from a group consistingof bivalent zinc (Zn(II)), bivalent iron (Fe (II)), bivalent nickel (Ni(II)), bivalent manganese (Mn (II)), bivalent cobalt (Co (II)), bivalenttin (Sn (II)), bivalent lead (Pb (II)), trivalent iron (Fe (III)),tetravalent molybdenum (Mo (IV)), hexavalent molybdenum (Mo (VI)),trivalent aluminum (Al (III)), pentavalent vanadium (V (V)), tetravalentvanadium (V (IV)), bivalent strontium (Sr (II)), tetravalent tungsten (W(IV)), hexavalent tungsten (W (VI)), bivalent copper (Cu (II)), andtrivalent chromium (Cr (III)), and

wherein X is selected from a group consisting of halogens, hydroxyl ion,sulfate ion, carbonate ion, cyanide ion, isocyanide ion, isothiocyanateion, carboxylate ion, and nitrate ion, and wherein n equals 1-3 and thecharges in chemical formula (II) are in balance.

The metal cyanide salt has a general formula expressed by chemicalformula (III):(M′)_(a)M(CN)_(b)(A)_(c)  (III)

wherein M in chemical formula (III) is selected from a group consistingof bivalent iron (Fe (II)), trivalent iron (Fe (III)), bivalent cobalt(Co (II)), trivalent cobalt (Co (III)), bivalent chromium (Cr (II)),trivalent chromium (Cr (III)), bivalent manganese (Mn (II)), trivalentmanganese (Mn (III)), trivalent iridium (Ir (III)), bivalent nickel (Ni(II)), trivalent rhodium (Rh (III)), bivalent ruthenium (Ru (II)),tetravalent vanadium (V (IV)), and pentavalent vanadium (V (V)), and

wherein M′ is selected from a group consisting of alkali metal ions andalkaline earth metal ions, and

wherein A is an anion which is selected from a group consisting ofhalides, hydroxyl ion, sulfate ion, carbonate ion, cyanide ion, oxalateion, thiocyanate isocyanide ion, isothiocyanate ion, carboxylate ion,and nitrate ion, and

wherein each of a and b is an integer greater than 1, and

wherein the sum of the charges of the groups subscripted by a, b and cis equal to the number of the charges of M.

In the abovementioned high-activity DMC catalyst, the fatty alcohol isone or more compounds selected from a group consisting of ethanol,n-propyl alcohol, isopropyl alcohol, n-butanol, isobutyl alcohol,sec-butyl alcohol, tert-butyl alcohol, 2-methyl-3-buten-2-ol, andtert-amyl alcohol.

In the abovementioned high-activity DMC catalyst, the alicycliccarbonate is selected from a group consisting of ethylene carbonate,propylene carbonate, 1,2-butylene carbonate, pentylene carbonate,hexylene carbonate, octylene carbonate, dodecylene carbonate, glycerolcarbonate, styrene carbonate, 3-phenyl propylene carbonate, cyclohexenecarbonate, vinyl ethylene carbonate, 4, 4-dimethyl-5-methylene-(1, 3)dioxolan-2-one, 4-allyl-4, 5-dimethyl-5-(10-undecenyl)-1,3-dioxolan-2-one.

The abovementioned high-activity DMC catalyst may further comprise atleast one functionalized compound or a water-soluble salt of thefunctionalized compound. The concentration of the functionalizedcompound or the water-soluble salt thereof in the high-activity DMCcatalyst is 2-80 wt %. The functionalized compound is defined to be acompound containing at least one functional group. The functional groupmay be selected from a group consisting of oxygen, nitrogen, sulfur,phosphorus, and halogens.

The present invention also proposes a method for fabricating thehigh-activity DMC catalyst, wherein two metal precursor solutions aremixed to react in the presence of the abovementioned organic complexingligand, and wherein at least one of the metal precursor solutionscontains a cyanide ligand. After the reaction, the solution is flushedand filtered repeatedly to remove the salts and separate thehigh-activity DMC catalyst from the solution.

In one embodiment, the organic complexing ligand exists in at least oneof the metal precursor solutions and fully mixes with the metalprecursor. Alternatively, the organic complexing ligand is added to thesolution immediately after two metal precursor solutions are mixed.

In one embodiment, a functionalized compound or the water-soluble saltof the functionalized compound is selectively added to the metalprecursor solution and/or the organic complexing ligand.

The present invention also proposes a method for fabricating polyols,wherein the high-activity DMC catalyst is used to enable a polyadditionreaction of at least one alkylene oxide and at least one startercompound containing active hydrogen atoms, whereby to generate thepolyols.

In one embodiment, the abovementioned polyaddition reaction isundertaken at a temperature of 25-200° C. and a pressure of 0.0001-20bar.

In one embodiment, the concentration of the high-activity DMC catalystin the polyaddition reaction is 0.0005-1 wt %.

Compared with the conventional DMC catalysts, the DMC catalyst of thepresent invention has higher activity and favors generating polyolshaving an insignificant amount of high-molecular-weight compounds.

Below, embodiments are described in detail to make easily understood theobjectives, technical contents, characteristics and accomplishments ofthe present invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flowchart of a method for fabricating a high-activity DMCcatalyst according to one embodiment of the present invention;

FIG. 2 is a flowchart of a method for fabricating polyols according toone embodiment of the present invention;

FIG. 3 is a diagram showing the GPC analysis spectrum of 6Kpolyoxypropylene triol, wherein the reactions for generating 6Kpolyoxypropylene triol uses the catalyst fabricated in Embodiment I: and

FIG. 4 is a diagram showing the GPC analysis spectrum of 6Kpolyoxypropylene triol, wherein the reactions for generating 6Kpolyoxypropylene triol uses the catalyst fabricated in Embodiment III.

DETAILED DESCRIPTION OF THE INVENTION

The present invention discloses a high-activity double-metal-cyanide(DMC) catalyst, which comprises at least one double-metal-cyanidecompound and at least one organic complexing ligand, wherein the organiccomplexing ligand is a mixture of a C2-C7 fatty alcohol and an alicycliccarbonate, and wherein the concentration of the fatty alcohol in theorganic complexing ligand is 2-98 mole %. The alicyclic carbonate of theorganic complexing ligand has a structural formula expressed by chemicalformula (I):

wherein R and R′ may be the same or different, and wherein each of R andR′ is selected from a group consisting of hydrogen atoms, saturatedalkyl groups each containing 1-20 carbon atoms, cyclic alkyl groups,hydroxyl groups, and vinyl groups.

The double metal cyanide of the abovementioned high-activitydouble-metal-cyanide catalyst is the product of the reaction of at leastone metal salt and at least one metal cyanide salt.

The metal salt has a general formula expressed by chemical formula (II):M(X)_(n)  (II)

In chemical formula (II), M may be but is not limited to be selectedfrom a group consisting of bivalent zinc (Zn(II)), bivalent iron (Fe(II)), bivalent nickel (Ni (II)), bivalent manganese (Mn (II)), bivalentcobalt (Co (II)), bivalent tin (Sn (II)), bivalent lead (Pb (II)),trivalent iron (Fe (III)), tetravalent molybdenum (Mo (IV)), hexavalentmolybdenum (Mo (VI)), trivalent aluminum (Al (III)), pentavalentvanadium (V (V)), tetravalent vanadium (V (IV)), bivalent strontium (Sr(II)), tetravalent tungsten (W (IV)), hexavalent tungsten (W (VI)),bivalent copper (Cu (II)), and trivalent chromium (Cr (III)), and

In chemical formula (II), X is an anion, which may be but is not limitedto be selected from a group consisting of halogens, hydroxyl ion,sulfate ion, carbonate ion, cyanide ion, isocyanide ion, isothiocyanateion, carboxylate ion, and nitrate ion.

In chemical formula (II), n equals 1-3, and the charges in chemicalformula (II) are in balance.

Specifically, the metal salt may be but is not limited to be selectedfrom a group consisting of zinc chloride, zinc sulfate, zinc bromide,zinc formate, zinc acetate, zinc propionate, zinc acetonylacetate, zincbenzoate, zinc nitrate, iron (II) sulfate, iron (II) bromide, cobalt(II) chloride, cobalt (II) thiocyanate, nickel (II) formate, nickel (II)nitrate, and the likes. The abovementioned metal salts may be usedsingly or jointly. Preferably, zinc halides are used as the metal salts.

The metal cyanide salt used by the present invention has a generalformula expressed by chemical formula (III):(M′)_(a)M(CN)_(b)(A)_(c)  (III)

In chemical formula (III), M may be but is not limited to be selectedfrom a group consisting of bivalent iron (Fe (II)), trivalent iron (Fe(III)), bivalent cobalt (Co (II)), trivalent cobalt (Co (III)), bivalentchromium (Cr (II)), trivalent chromium (Cr (III)), bivalent manganese(Mn (II)), trivalent manganese (Mn (III)), trivalent iridium (Ir (III)),bivalent nickel (Ni (II)), trivalent rhodium (Rh (III)), bivalentruthenium (Ru (II)), tetravalent vanadium (V (IV)), and pentavalentvanadium (V (V)). It is preferred: M is selected from a group consistingof bivalent cobalt (Co (II)), trivalent cobalt (Co (III)), bivalent iron(Fe (II)), trivalent iron (Fe (III)), trivalent chromium (Cr (III)),trivalent iridium (Ir (III)), and bivalent nickel (Ni (II)). Theabovementioned metals may be singly or jointly used as the metal of themetal cyanide salt.

In chemical formula (III), M′ is selected from a group consisting ofalkali metal ions and alkaline earth metal ions.

In chemical formula (III), A is an anion, which may be but is notlimited to be selected from a group consisting of halides, hydroxyl ion,sulfate ion, carbonate ion, cyanide ion, oxalate ion, thiocyanateisocyanide ion, isothiocyanate ion, carboxylate ion, and nitrate ion.

In chemical formula (III), each of a and b is an integer greater than 1,and the sum of the charges of the groups subscripted by a, b and c isequal to the number of the charges of M.

Specifically, the metal cyanide salt is selected from a group consistingof potassium hexacyanocobaltate (III), potassium hexacyanoferrate (II),potassium hexacyanoferrate (III), lithium hexacyanoiridate (III),lithium hexacyanocobaltate (III), sodium hexacyanocobaltate (III),calcium hexacyanocobaltate (III), cesium hexacyanocobaltate (III) andthe likes. The abovementioned metal cyanide salts may be used singly orjointly. Preferably, metal hexacyanocobaltate salts are used as themetal cyanide salts.

The double-metal-cyanide compound used by the present invention may bebut is not limited to be selected from a group consisting of zinchexacyanocobaltate(III), zinc hexacyanoferrate (II), zinchexacyanoferrate (III), nickel (II) hexacyanoferrate (II), cobalt (II)hexacyanocobaltate (III), and the likes. For other examples of thedouble-metal-cyanide compounds, please refer to the U.S. Pat. No.5,158,922. Preferably, zinc hexacyanocobaltate (III) is used as thedouble-metal-cyanide compound.

The organic complexing ligand used by the present invention is a mixtureof a C2-C7 fatty alcohol and an alicyclic carbonate. Specifically, thefatty alcohol is selected from a group consisting of ethanol, n-propylalcohol, isopropyl alcohol, n-butanol, isobutyl alcohol, sec-butylalcohol, tert-butyl alcohol, 2-methyl-3-buten-2-ol, tert-amyl alcohol,and the likes. The abovementioned fatty alcohols may be singly orjointly used. Preferably, the branched alcohols are used as the fattyalcohols, especially tert-butyl alcohol and 2-methyl-3-buten-2-ol.

Specifically, the alicyclic carbonate is selected from a groupconsisting of ethylene carbonate, propylene carbonate, 1,2-butylenecarbonate, pentylene carbonate, hexylene carbonate, octylene carbonate,dodecylene carbonate, glycerol carbonate, styrene carbonate, 3-phenylpropylene carbonate, cyclohexene carbonate, vinyl ethylene carbonate, 4,4-dimethyl-5-methylene-(1, 3) dioxolan-2-one, 4-allyl-4,5-dimethyl-5-(10-undecenyl)-1, 3-dioxolan-2-one, and the likes.

The organic complexing ligand used by the present invention, which isformed via mixing a fatty alcohol and an alicyclic carbonate, canenhance the activity of the DMC catalyst and decrease the amount ofhigh-molecular-weight compounds (whose average molecular weight isgreater than 400000) in the produced polyols. If an organic complexingligand does not contain any alicyclic carbonate but only contains fattyalcohol, the organic complexing ligand can also enhance the activity ofthe DMC catalyst, such as the technology disclosed by the U.S. Pat. No.5,470,813. However, the polyol produced by the conventional technologyhas too high an amount of high-molecular-weight (greater than 400000 inaverage) compounds in the produced polyol to meet expectation. If anorganic complexing ligand does not contain any fatty alcohol but onlycontains alicyclic carbonate, the activity of the DMC catalyst would besignificantly decreased. Besides, the range of the distribution of themolecular weights of the product is broadened, and the viscosity thereofis increased.

The present invention may modify the proportions of the fatty alcoholand the alicyclic carbonate in the organic complexing ligand to adjustthe activity of the DMC catalyst, the viscosity of the polyol, and thelike properties. The range of the concentration of the alicycliccarbonate in the organic complexing ligand is preferably 2-98 mole %,more preferably 5-95 mole %, most preferably 10-50 mole %.

The high-activity DMC catalyst disclosed by the present invention canoptionally contain at least one functionalized compound or thewater-soluble salt thereof. The functionalized compound is defined to bea compound having one or more functional groups. The functional groupmay be but is not limited to be selected from a group consisting ofoxygen, nitrogen, sulfur, phosphorus, and halogens. Specifically, thefunctionalized compound is selected from a group consisting ofpolyethers, polyesters, polycarbonates, polyalkylene glycol sorbitanesters, polyalkylene glycol glycidyl ethers, polyacrylamides,poly(acrylamide-co-acrylic acids), polyacrylic acids, poly(acrylicacid-co-maleic acid), poly(N-vinylpyrrolidone-co-acrylic acids),poly(acrylic acid-co-styrenes), salts of poly(acrylic acid-co-styrenes),maleic acids, styrenes and maleic anhydride copolymers, salts ofstyrenes and maleic anhydride copolymers, polyacrylonitriles, polyalkylacrylates, polyalkyl methacrylates, polyvinyl methyl ethers, polyvinylethyl ethers, polyvinyl acetates, polyvinyl alcohols,poly-N-vinylpyrrolidones, polyvinyl methyl ketones,poly(4-vinylphenols), oxazoline polymers, polyalkyleneimines,hydroxyethylcelluloses, polyacetals, glycidyl ethers, glycosides,carboxylic acid esters of polyhydric alcohols, bile acids, salts, estersand amides of bile acids, cyclodextrins, phosphorus compounds,unsaturated carboxylic acid ester, and ionic surface- orinterface-active compounds. The functionalized compound is preferablyselected from polyethers. Please also refer to the U.S. Pat. No.5,714,428 for other compounds suitable for the functionalized compoundof the present invention.

The solubility of the functionalized compound or the salt thereof towater or the solvent miscible with water is at least 3 wt %.Specifically, the solvent miscible with water is tetrahydrofuran,acetone, acetonitrile, tert-butyl alcohol, or the like. The solubilityof the functionalized compound or the salt thereof to water is veryimportant, determining whether the functionalized compound or the saltthereof can combine with double metal cyanide while double metal cyanideis formed and precipitated.

The concentration of the functionalized compound or the water-solublesalt thereof in the DMC catalyst is preferably 2-80 wt %, morepreferably 5-70 wt %, most preferably 10-60 wt %.

Refer to FIG. 1 a flowchart of a method for fabricating a high-activityDMC catalyst according to one embodiment of the present invention.

In Step S100, mix two metal precursor solutions to react in the presenceof the abovementioned fatty alcohol containing 2-7 carbon atoms and theabovementioned alicyclic carbonate to generate a resultant solution,wherein at least one of the metal precursor solutions contains a cyanideligand. The resultant solution contains a double-metal-cyanide compoundand an organic complexing ligand including the fatty alcohol and thealicyclic carbonate, wherein the alicyclic carbonate coordinates withthe double-metal-cyanide compound, wherein a concentration of the fattyalcohol in the organic complexing ligand is 2-98 mole %, and wherein thealicyclic carbonate has a structural formula expressed byabove-mentioned chemical formula (I). In one embodiment, the fattyalcohol and the alicyclic carbonate exist in at least one of the metalprecursor solutions and fully mix with the metal precursor; then the twometal precursor solutions are mixed. In one embodiment, none of the twometal precursor solutions has the fatty alcohol and the alicycliccarbonate; the fatty alcohol and the alicyclic carbonate are added tothe solution immediately after two metal precursor solutions are mixed;then precipitation is generated. In one embodiment, at least onefunctionalized compound or the water-soluble salt thereof is added tothe metal precursor solutions and/or the organic complexing ligand.

The combination of the abovementioned reactants may be achieved via anysuitable mixing method, such as a simple mixing method, a high-shearmixing method, a homogenization method, etc. Preferably, thehomogenization method or the high-shear mixing method is used to mix thereactants.

In the method for fabricating a high-activity DMC catalyst of thepresent invention, the metal precursor solutions are preferably mixed inan aqueous solution at a temperature of 10-80° C.

Next, the process proceeds to Step S110. In Step S110, repeat flushingand filtering the resultant solution of the reaction to remove saltsfrom the solution and remove the excess organic complexing ligand fromthe resultant solution to make free alicyclic carbonate be absent.

The high-activity DMC catalyst generated in the resultant solution canbe separated from the liquid using a known technology, such ascentrifugation, filtration, pressurized filtration, decanting, phaseseparation, or aqueous separation.

The aqueous solution of fatty alcohol, which is generated via mixingwater and fatty alcohol, may be used to flush the high-activity DMCcatalyst generated in the resultant solution. In one embodiment, theaqueous fatty alcohol solution contains at least one functionalizedcompound or a mixture or compound of at least two functionalizedcompounds. After the high-activity DMC catalyst has been flushed andseparated from the solution, an aqueous fatty alcohol solution or analcohol-containing aqueous solution is further used to flush thehigh-activity DMC catalyst, wherein the aqueous fatty alcohol solutionor the alcohol-containing aqueous solution has at least onefunctionalized compound or a mixture or compound of at least twofunctionalized compounds. A water-free solution is preferably used inthe final flushing step of the high-activity DMC catalyst.

In Step S120, separate the high-activity DMC catalyst without freealicyclic carbonate from the resultant solution.

The primary objective of the present invention is to provide ahigh-activity DMC catalyst. When synthesizing the high-activity DMCcatalyst, the alicyclic carbonate and the fatty alcohol play the role ofthe organic complexing ligand together in order to enhance the activityof the high-activity DMC catalyst. The alicyclic carbonate is onlycombined with a metal ion from the double-metal-cyanide compound, and nofree alicyclic carbonate will enter any subsequent reaction systemsusing the high-activity DMC as a catalyst.

The present invention further discloses a method for fabricatingpolyols, especially polyether polyols. Refer to FIG. 2 a flowchart of amethod for using a high-activity DMC catalyst to fabricate polyolsaccording to one embodiment of the present invention.

In Step S200, use the high-activity DMC catalyst of the presentinvention to catalyze a polyaddition reaction of one or more kinds ofalkylene oxides and one or more kinds of starter compounds having activehydrogen to generate polyols. The high-activity double-metal-cyanidecatalyst without free alicyclic carbonate makes free alicyclic carbonatebe absent in the polyaddition reaction.

The alkylene oxide preferably used by the present invention may be butis not to be selected from a group consisting of ethylene oxide,propylene oxide, butylene oxide, and the mixtures thereof. The polyetherchain of any kind of polyol can be formed via alkoxylating the monomersof a single kind of alkylene oxide, the monomers of 2-3 kinds ofalkylene oxides arranged arbitrarily, or the monomers of 2-3 kinds ofalkylene oxides arranged blockwise.

The starter compound having active hydrogen used by the presentinvention may be but is not limited to be a compound containing 1-8hydroxyl groups and having a weight average molecular weight (M) of18-2000, preferably 32-2000. Specifically, the starter compound havingactive hydrogen is selected from a group consisting of polyoxypropylenepolyols, polyoxyethylene polyols, poly(tetramethylene ether) glycols,glycerol, propoxylated glycerols, propylene glycol, tripropylene glycol,alkoxylated allylic alcohols, bisphenol A, pentaerythritol, sorbitol,sucrose, degraded starch, Mannich polyols, water, and combinationsthereof.

The starter compound having active hydrogen used by the presentinvention may be alkoxylated with any known method, which may be but isnot limited to be a batch-type process, a semi-batch type process or acontinuous type process. The alkoxylation is undertaken at a temperatureof 25-200° C., preferably 50-180° C., most preferably 60-150° C. Thealkoxylation is undertaken at a pressure of 0.0001-20 bar. Inalkoxylation, the amount of the added high-activity DMC catalyst shouldbe appropriately controlled to make the reaction fully controllableunder the provided reaction conditions. The concentration of thehigh-activity DMC catalyst in an ordinary reaction is preferably0.0005-1 wt %, more preferably 0.001-0.1 wt %, most preferably0.001-0.005 wt %.

The polyol fabricated by the present invention contains 1-8 hydroxylgroups, preferably 2-6 hydroxyl groups, most preferably 2-4 hydroxylgroups. The ratio of the alkylene oxide to the starter compound havingactive hydrogen correlates with the target molecular weight of thepolyols. The higher the ratio, the larger the molecular weight of thepolyol. In general, the range of the weight average molecular weights ofthe polyols is 500-100000 g/mole, preferably 1000-20000 g/mole, mostpreferably 2000-16000 g/mole.

While the high-activity DMC catalyst of the present invention is used infabricating polyols, the amount of high-molecular-weight (greater than400000 in average) compounds is decreased. Besides, the high-activityDMC catalyst of the present invention has higher reactivity than the DMCcatalysts disclosed in the conventional technologies. Thehigh-molecular-weight (greater than 400000 in average) compounds can bequantitatively measured in any appropriate method. The present inventionuses a gel permeation chromatography (GPC) method. The GPC equipment isprovided by Waters Cooperation Taiwan, including the analyzer ACQUITYAPC System and the detector ACQUITY ELSD. The column assembly thereofincludes ACQUITY APC XT 45 Å, 1.7 μm, 4.6 mm×150 mm, ACQUITY APC XT 125Å, 2.5 μm, 4.6 mm×150 mm, and ACQUITY APC XT 200 Å, 2.5 μm, 4.6 mm×150mm, which are connected in series. In the analysis of thehigh-molecular-weight compounds in polyols, the polystyrene havingmolecular weights of 20000-1000000 is used to produce the calibrationcurve; the limit of the quantitative analysis is 5 ppm; the range ofdetected molecular weights is 1000-2000000.

Below, several embodiments are provided to further demonstrate how tofabricate the high-activity DMC catalyst of the present invention, howto use the catalyst of the present invention to catalyze thepolyaddition reaction of alkylene oxides and starter compounds havingactive hydrogen to generate polyols.

Embodiment I

Use ethylene carbonate (EC) and tert-butyl alcohol (TBA) as the organiccomplexing ligand to fabricate the high-activity DMC catalyst:

Mix 94 g zinc chloride (ZnCl₂), 33 g ethylene carbonate (EC), 176 gtert-butyl alcohol (TBA), and 1375 g water to form Solution A; mix 38 gpotassium hexacyanocobaltate (III) (K₃Co(CN)₆), 13 g ethylene carbonate(EC), 71 g tert-butyl alcohol (TBA), and 500 g water to form Solution B;mix Solution A and Solution B and agitate them uniformly at an ambienttemperature to generate a white solid in the solution; use pressurizedfiltration to separate the solid from the solution; add the solid to amixture solution of 508 g tert-butyl alcohol (TBA) and 275 g water, andagitate them at an ambient temperature to disperse the solid uniformlyin the solution; use pressurized filtration to separate the solid fromthe solution; add the solid to 723 g tert-butyl alcohol (TBA) andagitate them at an ambient temperature to disperse the solid uniformlyin the solution; use pressurized filtration to separate the solid fromthe solution; dry the solid in vacuum at a temperature of 60° C. toobtain the high-activity DMC catalyst.

Embodiment II

Use ethylene carbonate (EC) and tert-butyl alcohol (TBA) as the organiccomplexing ligand to fabricate the high-activity DMC catalyst:

Embodiment II is the same as Embodiment I except the changes statedbelow: ethylene carbonate (EC) is changed to be 51 g and tert-butylalcohol (TBA) is changed to be 159 g in Solution A; ethylene carbonate(EC) is changed to be 20 g and tert-butyl alcohol (TBA) is changed to be64 g in Solution B.

Embodiment III

Use ethylene carbonate (EC) and tert-butyl alcohol (TBA) as the organiccomplexing ligand and add polypropylene glycol (PPG) to fabricate thehigh-activity DMC catalyst:

Mix 94 g zinc chloride (ZnCl₂), 33 g ethylene carbonate (EC), 176 gtert-butyl alcohol (TBA), and 1375 g water to form Solution A; mix 38 gpotassium hexacyanocobaltate (III) (K₃Co(CN)₆), 13 g ethylene carbonate(EC), 71 g tert-butyl alcohol (TBA), and 500 g water to form Solution B;mix 40 g polypropylene glycol (PPG) having a molecular weight of 400, 9g tetrahydrofuran (THF), and 500 g water to form Solution C; mixSolution A and Solution B and agitate them uniformly at an ambienttemperature to form a mixture solution; add Solution C to the mixturesolution of Solution A and Solution B and agitate them for 3 minutes;use pressurized filtration to separate a solid from the solution; addthe solid to a mixture solution containing 10 g polypropylene glycol(PPG) having a molecular weight of 400, 9 g tetrahydrofuran (THF), 508 gtert-butyl alcohol (TBA), and 275 g water, and agitate them at anambient temperature to disperse the solid uniformly in the solution; usepressurized filtration to separate the solid from the solution; add thesolid to a mixture solution containing 5 g polypropylene glycol (PPG)having a molecular weight of 400, 9 g tetrahydrofuran (THF), and 723 gtert-butyl alcohol (TBA), and agitate them at an ambient temperature todisperse the solid uniformly in the solution; use pressurized filtrationto separate the solid from the solution; dry the solid in vacuum at atemperature of 60° C. to obtain the high-activity DMC catalyst.

Comparison I

Use Tert-Butyl Alcohol (TBA) as the Organic Complexing Ligand toFabricate the High-Activity DMC Catalyst:

Mix 100 g zinc chloride (ZnCl₂), 388 g tert-butyl alcohol (TBA), and1000 g water to form Solution A; mix 40 g potassium hexacyanocobaltate(III) (K₃Co(CN)₆) and 400 g water to form Solution B; mix Solution A andSolution B and agitate them uniformly at an ambient temperature togenerate a white solid in the solution; use pressurized filtration toseparate the solid from the solution; add the solid to a mixturesolution of 680 g tert-butyl alcohol (TBA) and 375 g water, and agitatethem at an ambient temperature to disperse the solid uniformly in thesolution; use pressurized filtration to separate the solid from thesolution; add the solid to 970 g tert-butyl alcohol (TBA) and agitatethem at an ambient temperature to disperse the solid uniformly in thesolution; use pressurized filtration to separate the solid from thesolution; dry the solid in vacuum at a temperature of 60° C. to obtainthe high-activity DMC catalyst.

Comparison II

Use Tert-Butyl Alcohol (TBA) as the Organic Complexing Ligand and AddPolypropylene Glycol (PPG) to Fabricate the High-Activity DMC Catalyst:

Mix 100 g zinc chloride (ZnCl₂), 388 g tert-butyl alcohol (TBA), and 750g water to form Solution A; mix 40 g potassium hexacyanocobaltate (III)(K₃Co(CN)₆) and 400 g water to form Solution B; mix 40 g polypropyleneglycol (PPG) having a molecular weight of 400, 8 g tert-butyl alcohol(TBA), and 250 g water to form Solution C; mix Solution A and Solution Band agitate them uniformly at an ambient temperature to form a mixturesolution; add Solution C to the mixture solution of Solution A andSolution B and agitate them for 3 minutes; use pressurized filtration toseparate a solid from the solution; add the solid to a mixture solutioncontaining 10 g polypropylene glycol (PPG) having a molecular weight of400, 680 g tert-butyl alcohol (TBA), and 375 g water, and agitate themat an ambient temperature to disperse the solid uniformly in thesolution; use pressurized filtration to separate the solid from thesolution; add the solid to a mixture solution containing 5 gpolypropylene glycol (PPG) having a molecular weight of 400 and 970 gtert-butyl alcohol (TBA), and agitate them at an ambient temperature todisperse the solid uniformly in the solution; use pressurized filtrationto separate the solid from the solution; dry the solid in vacuum at atemperature of 60° C. to obtain the high-activity DMC catalyst.

Evaluation of the Catalyzing Activity of the Catalyst: SynthesizingPolyether Polyol

Embodiment IV

The method for fabricating polyoxypropylene diol having a molecularweight of 2000:

Add 750 g polypropylene glycol (PPG) as the starter compound (having ahydroxyl value=280 mg KOH/g) and 50 ppm (with respect to the totalweight of products) catalyst to a pressure-resistant reactor, and heatthe reactants to 120° C. under a nitrogen environment with persistentagitation; undertake the first stage of propylene oxide (PO) additionand add 225 g PO to the reactor; while the pressure of the reactorbegins to decrease (it means that the catalyst has been activated),undertake the second stage of PO addition and add 2891 g PO to thereactor in a continuous feeding way; after the PO addition is completed,continuously agitate the reactants for 30 minutes at a temperature of120° C.; let the reactor cool down to the ambient temperature; take outthe product—polyether polyol for evaluation. The induction time of thecatalyst is defined to be the time interval between the time point ofthe first stage of PO addition and the time point at which the pressureof the reactor begins to decrease. The activity of the catalyst isdefined to be the amount of the propylene oxide catalyzed to bepropoxylated by each gram of the catalyst each minute. The results areshown in Table. 1.

Embodiment V

The Method for Fabricating Polyoxypropylene Triol Having a MolecularWeight of 6000:

Embodiment V is essentially the same as Embodiment IV except the changesstated below: the starter compound is changed from 750 g polypropyleneglycol (PPG) (having a hydroxyl value=280 mg KOH/g) to 650 gpropoxylated glycerin (having a hydroxyl value=240 mg KOH/g); the amountof PO added in the first stage is changed to be 110 g; the amount of POadded in the second stage is changed to be 4875 g. The results are shownin Table 2.

Table 1 showing results of the reactions where catalysts catalyze thepropoxylation of polypropylene glycol to generate polyether polypol ( 2Kpolyoxypropylene diol) Catalyst features 2K mw polyoxypropylene diolInduction Activity Double-bond Polydispersity Organic time (kg PO/gViscosity amount Index Catalyst complexing ligand (min) Cat./min)(cps@25° C.) (meq/g) (Mw/Mn) E^(a) I EC 15 wt % + TBA 14 228 319.4 0.0071.03 E II EC 24 wt % + TBA 111 197 359.2 0.004 1.04 E III EC 15 wt % +TBA + PPG 2 294 295.4 0.007 1.03 C^(b) I TBA 25 17.2 333.3 0.004 1.04 CII PPG + TBA 33 149 319.4 0.004 1.03 ^(a)Embodiment ^(b)Comparison

Table 2 showing results of the reactions where catalysts catalyze thepropoxylation of polypropylene glycol to generate polyether polypol ( 6Kpolyoxypropylene triol) Catalyst features 6K mw polyoxypropylene triolInduction Activity Double-bond polydispersity Organic time (kg PO/gViscosity amount Index Catalyst complexing ligand (min) Cat./min)(cps@25° C.) (meq/g) (Mw/Mn) E^(a) I EC + TBA 26 166 1184.1 0.001 1.07 EIII EC + PPG + TBA 14 130 1134.7 0.004 1.03 C^(b) I TBA 27 20 1190.20.006 1.06 C II PPG + TBA 16 110 1131.8 0.002 1.05 ^(a)Embodiment^(b)Comparison

Refer to FIG. 3 and FIG. 4 for the GPC analysis spectra of 6Kpolyoxypropylene triol, wherein the reactions for generating 6Kpolyoxypropylene triol respectively use the catalysts fabricated inEmbodiment I and Embodiment III.

It is seen in the results of Embodiment I and Embodiment II (shown inTable 1): the method for fabricating high-activity DMC catalyst of thepresent invention can vary the amount of added ethylene carbonate tocontrol the features of the catalyst and modify the characteristics ofthe polyol product.

It is seen in the results of Embodiment I and Embodiment III, ComparisonI and Comparison II (shown in Table 1, Table 2, FIG. 3 , and FIG. 4 ):the high-activity DMC catalyst of the present invention has highercatalyzing activity than the DMC catalysts of the conventionaltechnologies, not only having a shorter catalyst induction time but alsocatalyzing the propoxylation of a higher amount of propylene oxide perunit time; the polyether polyols generated by the present invention hasan insignificant amount of high-molecular-weight compounds for theconcentration detection limit of 5 ppm and the molecular weightdetection range of 1000-2000000.

Please refer to Table 1 and Table 2, in the test of the propylene oxidebeing polymerized to produce the polyether polyols, the required“induction time” in the early stage of the reaction can be greatlyshorten by using DMC synthesized by adding EC as a catalyst. Thisclearly indicates that the added EC by the catalyst technology asdisclosed above mainly has a significant effect on the high-activity DMCcatalyst produced. Also, its catalytic “activity” has a significantcorrelation with the amount of the added EC.

In addition, please refer to the Table 3 below. It clearly shows thatwith the preparation of the catalyst, the increase in the amount of ECadded as an organic complexing ligand does not have a significant effecton the polyether polyol produced by the propylene oxide polymerizationusing the high-activity DMC catalyst as the catalyst. There does nothave any carbonate groups and ethyleneoxy groups in the structure of thepolyether polyol, and there does not have much difference for thecontent of the Primary OH of the polyether polyol. This means that theadded EC in the high-activity DMC catalyst synthesis method as disclosedby the present invention does not participate in any subsequentreactions using the high-activity DMC as a catalyst.

Table 3 Showing Results of the Reactions where Catalysts Catalyze thePropoxylation of Polypropylene Glycol to Generate Polyether Polyol (2KPolyoxypropylene Diol)

Product: polyether polyol Preparation of Catalyst: (Mw = 2000) organiccomplexing ligand Weight % Content of organic carbonate ethylene PrimaryOH complexing ligand groups/molecule oxy groups content % C^(b) I EC 0wt % + TBA 0.0 0.0 8.9 E^(a) I EC 15 wt % + TBA 0.0 0.0 8.6 E II EC 24wt % + TBA 0.0 0.0 8.8 ^(a)Embodiment ^(b)Comparison

The function of adding the alicyclic carbonate when synthesizing thehigh-activity DMC catalyst in the present invention is to enhance theactivity of the catalyst, not to participate in the subsequent catalyticreaction. The alicyclic carbonate only participates in the reaction whensynthesizing the high-activity DMC catalyst. Therefore, the alicycliccarbonate will affect the activity of the high-activity DMC catalyst tomake the high-activity DMC catalyst have the higher “Activity” (SeeTable 1 and Table 2) and the shorter “Induction time” (See Table 2)during the synthesis of the polyether polyols. The alicyclic carbonatedoes not participate in the reaction when subsequently used in thesynthesis of polyether polyols. Therefore, the physical properties ofthe synthesized polyether polyols (such as Viscosity, Double-bond amount& Polydispersity Index) will not be significantly affected (See Table 1and Table 2).

In conclusion, the present invention proposes a high-activitydouble-metal-cyanide catalyst, a method for fabricating the same, andapplications of the same to fabricate polyols. The present invention canenhance the activity of the DMC catalyst via merely adding alicycliccarbonate to the conventional catalyst synthesis process. Further, thepresent invention can be used to generate polyols having lesshigh-molecular-weight compounds. Therefore, the present invention isvery useful in industry.

The embodiments described above are only to exemplify the presentinvention but not to limit the scope of the present invention. Anyequivalent modification or variation according to the characteristic orspirit of the present invention is to be also included by the scope ofthe present invention.

What is claimed is:
 1. A method for fabricating a high-activitydouble-metal-cyanide catalyst comprises: mixing two metal precursorsolutions to react in the presence of a fatty alcohol containing 2-7carbon atoms and an alicyclic carbonate, to generate a resultantsolution, wherein at least one of said two metal precursor solutionscontains a cyanide ligand, wherein said resultant solution comprises adouble-metal-cyanide compound and an organic complexing ligand includingsaid fatty alcohol and said alicyclic carbonate, wherein said alicycliccarbonate coordinates with said double-metal-cyanide compound, wherein aconcentration of said fatty alcohol in said organic complexing ligand is2-98 mole %, and wherein said alicyclic carbonate has a structuralformula expressed by chemical formula (I):

wherein R and R′ are identical or different, and wherein each of R andR′ is selected from a group consisting of hydrogen atoms, saturatedalkyl groups each containing 1-20 carbon atoms, cyclic alkyl groups,hydroxyl groups, and vinyl groups; flushing and filtering said resultantsolution to remove excess organic complexing ligand from said resultantsolution to make free alicyclic carbonate be absent; and separating saidhigh-activity double-metal-cyanide catalyst without free alicycliccarbonate from said resultant solution.
 2. The method for fabricating ahigh-activity double-metal-cyanide catalyst according to claim 1,wherein said fatty alcohol and said alicyclic carbonate exists in atleast one of said two metal precursor solutions and mixes with a metalprecursor; alternatively, said fatty alcohol and said alicycliccarbonate is added to said resultant solution immediately after said twometal precursor solutions are mixed.
 3. The method for fabricating ahigh-activity double-metal-cyanide catalyst according to claim 2,further comprising mixing at least one functionalized compound with saidtwo metal precursor solutions to react in the presence of said fattyalcohol and said alicyclic carbonate to generate a resultant solution,wherein said at least one functionalized compound is a compoundcontaining at least one functional group, and wherein said at least onefunctional group is selected from a group consisting of oxygen,nitrogen, sulfur, phosphorus, and halogens.
 4. The method forfabricating a high-activity double-metal-cyanide catalyst according toclaim 3, wherein a concentration of said at least one functionalizedcompound in said high-activity double-metal-cyanide catalyst is 2-80 wt%.
 5. The method for fabricating a high-activity double-metal-cyanidecatalyst according to claim 4, wherein said at least one functionalizedcompound is selected from a group consisting of polyethers, polyesters,polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycolglycidyl ethers, polyacrylamides, poly(acrylamide-co-acrylic acids),polyacrylic acids, poly(acrylic acid-co-maleic acid),poly(N-vinylpyrrolidone-co-acrylic acids), poly(acrylicacid-co-styrenes), salts of poly(acrylic acid-co-styrenes), maleicacids, styrenes and maleic anhydride copolymers, salts of styrenes andmaleic anhydride copolymers, polyacrylonitriles, polyalkyl acrylates,polyalkyl methacrylates, polyvinyl methyl ethers, polyvinyl ethylethers, polyvinyl acetates, polyvinyl alcohols,poly-N-vinylpyrrolidones, polyvinyl methyl ketones,poly(4-vinylphenols), oxazoline polymers, polyalkyleneimines,hydroxyethylcelluloses, polyacetals, glycidyl ethers, glycosides,carboxylic acid esters of polyhydric alcohols, bile acids, salts, estersand amides of bile acids, cyclodextrins, phosphorus compounds, andunsaturated carboxylic acid esters.
 6. The method for fabricating ahigh-activity double-metal-cyanide catalyst according to claim 2,wherein said two metal precursor solutions are mixed to react in anaqueous solution, and wherein said aqueous solution is at a temperatureof 10-80° C.
 7. The method for fabricating a high-activitydouble-metal-cyanide catalyst according to claim 1, wherein said twometal precursor solutions includes a metal salt and a metal cyanidesalt, wherein said metal salt has a general formula expressed bychemical formula (II):M(X)_(n)  (II) wherein M in chemical formula (II) is selected from agroup consisting of bivalent zinc (Zn(II)), bivalent iron (Fe (II)),bivalent nickel (Ni (II)), bivalent manganese (Mn (II)), bivalent cobalt(Co (II)), bivalent tin (Sn (II)), bivalent lead (Pb (II)), trivalentiron (Fe (III)), tetravalent molybdenum (Mo (IV)), hexavalent molybdenum(Mo (VI)), trivalent aluminum (Al (III)), pentavalent vanadium (V (V)),tetravalent vanadium (V (IV)), bivalent strontium (Sr (II)), tetravalenttungsten (W (IV)), hexavalent tungsten (W (VI)), bivalent copper (Cu(II)), and trivalent chromium (Cr (III)), and wherein X is selected froma group consisting of halogens, hydroxyl ion, sulfate ion, carbonateion, cyanide ion, isocyanide ion, isothiocyanate ion, carboxylate ion,and nitrate ion, and wherein n equals 1-3 and charges in chemicalformula (II) are in balance, and wherein said metal cyanide salt has ageneral formula expressed by chemical formula (III):(M′)_(a)M(CN)_(b)(A)_(c)  (III) wherein M in chemical formula (III) isselected from a group consisting of bivalent iron (Fe (II)), trivalentiron (Fe (III)), bivalent cobalt (Co (II)), trivalent cobalt (Co (III)),bivalent chromium (Cr (II)), trivalent chromium (Cr (III)), bivalentmanganese (Mn (II)), trivalent manganese (Mn (III)), trivalent iridium(Ir (III)), bivalent nickel (Ni (II)), trivalent rhodium (Rh (III)),bivalent ruthenium (Ru (II)), tetravalent vanadium (V (IV)), andpentavalent vanadium (V (V)), and wherein M′ is selected from a groupconsisting of alkali metal ions and alkaline earth metal ions, andwherein A is an anion which is selected from a group consisting ofhalides, hydroxyl ion, sulfate ion, carbonate ion, cyanide ion, oxalateion, thiocyanate isocyanide ion, isothiocyanate ion, carboxylate ion,and nitrate ion, and wherein each of a and b is an integer greater than1, and wherein a sum of charges of groups subscripted by a, b and c isequal to a number of charges of M.
 8. The method for fabricating ahigh-activity double-metal-cyanide catalyst according to claim 7,wherein M in chemical formula (II) is selected from a group consistingof bivalent zinc (Zn(II)), bivalent iron (Fe (II)) and bivalent cobalt(Co (II)), and wherein M in chemical formula (III) is selected from agroup consisting of bivalent cobalt (Co (II)), trivalent cobalt (Co(III)), bivalent iron (Fe (II)), trivalent iron (Fe (III)), trivalentchromium (Cr (III)), trivalent iridium (Ir (III)) and bivalent nickel(Ni (II)).
 9. The method for fabricating a high-activitydouble-metal-cyanide catalyst according to claim 7, wherein said metalsalt is selected from a group consisting of zinc chloride, zinc sulfate,zinc bromide, zinc formate, zinc acetate, zinc propionate, zincacetonylacetate, zinc benzoate, zinc nitrate, iron (II) sulfate, iron(II) bromide, cobalt (II) chloride, cobalt (II) thiocyanate, nickel (II)formate, and nickel (II) nitrate, and wherein said metal cyanide salt isselected from a group consisting of potassium hexacyanocobaltate (III),potassium hexacyanoferrate (II), potassium hexacyanoferrate (III),lithium hexacyanoiridate (III), lithium hexacyanocobaltate (III), sodiumhexacyanocobaltate (III), calcium hexacyanocobaltate (III), and cesiumhexacyanocobaltate (III).
 10. The method for fabricating a high-activitydouble-metal-cyanide catalyst according to claim 7, wherein saiddouble-metal-cyanide compound is selected from a group consisting ofzinc hexacyanocobaltate (III), zinc hexacyanoferrate (II), zinchexacyanoferrate (III), nickel (II) hexacyanoferrate (II), and cobalt(II) hexacyanocobaltate (III).
 11. The method for fabricating ahigh-activity double-metal-cyanide catalyst according to claim 1,wherein said fatty alcohol is one or more compounds selected from agroup consisting of ethanol, n-propyl alcohol, isopropyl alcohol,n-butanol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol,2-methyl-3-buten-2-ol, and tert-amyl alcohol, and wherein said alicycliccarbonate is selected from a group consisting of ethylene carbonate,propylene carbonate, 1,2-butylene carbonate, pentylene carbonate,hexylene carbonate, octylene carbonate, dodecylene carbonate, glycerolcarbonate, styrene carbonate, 3-phenyl propylene carbonate, cyclohexenecarbonate, vinyl ethylene carbonate, 4, 4-dimethyl-5-methylene-(1, 3)dioxolan-2-one, and 4-allyl-4, 5-dimethyl-5-(10-undecenyl)-1,3-dioxolan-2-one.
 12. The method for fabricating a high-activitydouble-metal-cyanide catalyst according to claim 1, wherein aconcentration of said alicyclic carbonate in said organic complexingligand ranges from 2 to 98 mole %.